Method for preparing oxyhydrocarbylnorbornane derivatives

ABSTRACT

Processes and compositions are described for the use in perfume aroma augmenting, enhancing, modifying and imparting compositions and as perfume and perfumed article aroma imparting and enhancing materials of oxyhydrocarbylnorbornanes having the structure: ##STR1## wherein X is carbonyl or carbinyl having the structures, respectively: ##STR2## and wherein at least one of the dashed lines is a carbon-carbon single bond and the other of the dashed lines is a carbon-carbon single bond or a carbon-carbon double bond. Addition of the said oxyhydrocarbylnorbornanes to consumable materials is indicated to produce in perfumes, colognes and perfumed articles, natural, sweet pine, incense, camphene-like, sweet, green, floral, fruity, dried fruity, ionone-like, orris-like and nasturtium-like aromas with dried, woody, piney, sweaty, geranic acid-like nuances.

This is a divisional of application Ser. No. 860,124, filed 12/13/77,now U.S. Pat. No. 4,186,150 which application is a continuation-in-partof United States Application for Letters Patent Ser. No. 765,847, filedon Feb. 4, 1977, now U.S. Pat. No. 4,076,853.

BACKGROUND OF THE INVENTION

The present invention relates to oxyhydrocarbylnorbornanes andcompositions using said oxyhydrocarbylnorbornanes which have the genericstructure: ##STR3## wherein at least one of the dashed lines is acarbon-carbon single bond and the other of the dashed lines is acarbon-carbon single bond or a carbon-carbon double bond and X iscarbonyl having the structure: ##STR4## or carbinyl having thestructure: ##STR5## to augment or enhance the aroma of perfumecompositions, perfumed articles and colognes or to impart aroma to suchperfume compositions, perfumed articles or colognes.

There has been considerable work performed relating to substances whichcan be used to impart (modify, augment or enhance) fragrances to (or in)various consumable materials such as perfume compositions, colognes andperfumed articles including soaps, detergents, cosmetics and powders.These substances are used to diminish the use of natural materials, someof which may be in short supply and to provide more uniform propertiesin the finished product.

Natural, sweet pine, incense, camphene-like, sweet, green, floral,fruity, dried fruity, ionone-like, orris-like and nasturtium-like aromaswith dried, woody, piney, sweaty and geranic acid-like nuances areparticularly desirable in several types of perfume compositions,perfumed articles and colognes.

U.S. Pat. No. 3,852,358 issued on Dec. 3, 1974 discloses a process forproducing 2-acetyl-3,3-dimethyl-5-norbornene in both the exo and endoforms which have uses in perfumery and other fragrance applications.These compounds have the structures: ##STR6## These compounds, producedby reaction of cyclopentadiene with mesityl oxide, are startingmaterials for producing a number of the compounds of our invention.However, the compounds of our invention have unexpected, unobvious andadvantageous properties when compared with the2-acetyl-3,3-dimethyl-5-norbornene of U.S. Pat. No. 3,852,358.

U.S. Pat. No. 3,942,761 discloses the use in perfumery of4(2'-norbornyl)-2-butanones having the structure: ##STR7## wherein R₁ ishydrogen or methyl and R is hydrogen or lower alkyl containing from 1 to8 carbon atoms. Such compounds have structures which are different inkind from the structures of the compounds of our invention. Alsodisclosed as intermediates for producing the foregoing compounds arecompounds having the generic structure: ##STR8## wherein the dotted lineis a carbon-carbon single bond or a carbon-carbon double bond. Inaddition, the following reaction sequence is set forth therein: ##STR9##

Arctander, "Perfume and Flavor Chemicals", 1969, Vol. 1, discloses theuse in perfume compositions and in foodstuff flavors of "fenchone","fenchyl alcohol", "camphene carbinol", and "camphene carbinyl acetate",thus:

(i) "1385: FENCHONE

laevo-Fenchone. (dextro- is known but less common as a fragrancematerial).

1,3,3-Trimethyl-2-norbornanone.

1,3,3-Trimethyl bicyclo-1,2,2-heptanone-2. ##STR10## Warm-camphoraceous,powerful and diffusive, basically sweet odor. Warm, somewhat burning andbitter taste with a medicinal note.

This ketone finds some use as a masking odor in industrial fragrances.It is also used in the reconstruction of Fennel oil and a few otheressential oils.

In spite of its rather unpleasant taste, it is used in various Berrycomplex flavors, in Spice complexes and in certain types of Liquerflavoring.

The concentration used is about 0.1 to 5 ppm in the finished product."

(ii) "1387: FENCHYL ALCOHOL

1,3,3-Trimethyl-2-norbornanol.

1,3,3-Trimethyl bicyclo-1,2,2-heptanol-2.

2-Fenchanol.

Fenchol. ##STR11## Powerful and diffusive, Camphor-like, but sweeter andmore Citrus-like almost Lime-like odor with more or less of anearthy-dry character, according to the composition and isomer-ratio.

The taste is somewhat bitter-Lime-like, camphoraceous and slightlywoody-musty.

This interesting alcohol (or mixed alcohols) finds use in perfumecompositions ranging from woody or herbaceous to Citrus-Lime and evencertain floral types. It produces power and "lift" to floral fragrances,and solid background to Lime and other Citrus bases, having theadvantage over the Terpenes in being very stable in soap.

Fenchyl alcohol is also used in flavor compositions such as Strawberryand other berries, Lime and Spice, etc.

The concentration is normally low, e.g., 0.2 up to 5 ppm in the finishedproduct."

(iii) "1028: 3,3-DIMETHYL-Δ², beta-NORBORNANE-2-ETHANOL

"Camphene carbinol". ##STR12## Sweet-camphoraceous, warm and soft odorwith a woody undertone. Upon standing it may develop an odor resemblingthat of Celluloid.

Although rarely offered commercially, this chemical could find some usein perfume compositions of the woody, Oriental and orrisy type, in newvariations of Pine fragrances, and in various soap and detergentperfumes."

(iv) "1029: 3,3-DIMETHYL-Δ² -beta-NORBORNANE-2-ETHYLACETATE

"Camphene carbinyl acetate". ##STR13## Mild and sweet-woody odor with afloral-piney undertone. The commercial products are probably notwell-defined single chemicals, and great variations in odor have beenobserved.

This ester has been developed in line with the research on Sandalwoodtype odors. The parent alcohol "Camphene carbinol" was once considereduseful as a Sandalwood type material, but it has found more use as asweetening and enriching ingredient in sophisticated Pine fragrances.The title ester finds limited use in perfume compositions of woodycharacter, Fougeres, Pine fragrances, etc. and it blends very well withthe Cyclohexanol derivatives, Ionones, iso-Bornylacetate, Nitromusks,etc."

U.S. Pat. No. 3,928,456 discloses monocyclic compounds having thegeneric structure: ##STR14## containing one double bond in position 2'-or 3'- of the acyl side-chain and either one double bond in position 1-or 2- (as shown in the above formula, the double bond in the 2 positioncan be either in the cycle or the side chain), or two conjugated doublebonds in positions 1- and 3- of the cycle, the double bonds beingrepresented by dotted lines, and wherein n is zero or 1, R¹, R² and R³represent hydrogen or one of them a lower alkyl radical, such as methylor ethyl, and the others hydrogen, and R⁴, R⁵, R⁶ and R⁷ representhydrogen or one of them a lower alkyl radical, such as methyl or ethyl,and the others hydrogen, as being useful in perfumery and food flavorsand also flavors, beverages, animal feeds and tobaccos. Specificallydisclosed in this patent in a compound having the structure: ##STR15##

U.S. Application for Letter Patent Ser. No. 551,030, filed on Feb. 19,1975 and now U.S. Pat. No. 4,000,050, discloses, interalia, perfumeryuses of compounds having the structures: ##STR16## wherein one of thedashed lines is a carbon-carbon bond and each of the wavy lines in acarbon-carbon single bond, one of the carbon-carbon single bondsrepresented by the wavy line being epimeric with respect to the other ofthe carbon-carbon single bonds represented by the wavy line.

In addition, various processes and compounds relating to the synthesisof synthetic sandalwood oil components are described in the followingU.S. Patents:

(i) Perfume Compounds and Process for Preparing Same--U.S. Pat. No.3,673,261, issued June 27, 1972:

Compounds ##STR17## (ii) Dihydro-β-santalol and Processes for PreparingDihydro-β-santalol from 3-Endo-Methyl-3-Exo(4'-Methyl-5'-Hydroxyphenyl)Norcamphor--U.S. Pat. No. 3,673,263, issued June 27, 1972: ##STR18##(iii) Process for Preparing β-Santalol from 3-Methylnorcamphor--U.S.Pat. No. 3,662,008, issued May 9, 1972: ##STR19## (iv) Process forPreparing Dihydro-β-Santalol from3-Endo-Methyl-3-Exo(4'-Methyl-5'-Hydroxypentyl) Norcamphor--U.S. Pat.No. 3,673,266, issued June 27, 1972: ##STR20##

None of the compounds disclosed in either U.S. Pat. No. 3,928,456 orU.S. Application for Letters Patent Ser. No. 551,030, filed Feb. 19,1975 and now U.S. Pat. No. 4,000,050 have properties even closelysimilar to the properties of the "oxyhydrocarbylnorbornanes" of theinstant application.

Chem. Abstracts, Vol. 84, 73728n (abstract of Karaev, et al.Zh.Org.Khim. 1975, 11(12), 2622) discloses preparation of the compound:##STR21##

Klein and Rojahn, Chem. Abstracts, Vol. 84, 90327y (1976) discloses theuse of compounds having the generic structure: ##STR22## (wherein thedashed line is a single or double bond) as an intermediate in thepreparation of β-santalol; but no organoleptic properties of thesenorbornane derivatives are disclosed.

U.S. Pat. No. 3,748,344, issued on July 24, 1973, discloses thatchemical compounds characterized by the structural formula: ##STR23##wherein the dashed line represents the presence of a single or a doublebond wherein R₁ ', R₂ ', R₃ ' and R₄ ' each represent hydrogen or lowermethyl and R₅ ' represents hydrogen or lower alkyl and R₆ ' represents apolymethylene radical of from 2 to 4 carbon atoms which is unsubstitutedor substituted with lower alkyl, which "as a whole exhibits acharacteristic, pleasant, strong and long lasting aroma which is highlyuseful in the preparation of fragrance compositions and perfumeproducts". Various notes are described such as green, cuminic, walnut,raw potato, earthy, camphoraceous, civet, walnut bark, neroli, anise,vegetable, mnthone, animal, minty, eucalyptol, cucumber, pine and fecal.

In addition, U.S. Pat. No. 3,748,344 discloses as chemical intermediatesfor preparing the above ketal, a compound having the generic structure:##STR24## wherein R₁ ', R₂ ', R₃ ', R₄ ' and R₅ ' have the same meaningas defined above.

However, the specific compound of our invention is not set forth in U.S.Pat. No. 3,748,344.

No prediction of the organoleptic properties of the compound of theinstant invention can be made by a study of the disclosure of U.S. Pat.No. 3,748,344.

Chemical Abstracts, Vol. 71, 49664z (abstract of Sadykh-Zade, et al.(U.S.S.R.) Dokl. Akad. Nauk Azerb. SSR 1968, 24(11), 38-41) disclosesthe synthesis of exo and endo forms of the compounds having thestructures: ##STR25##

Chemical Abstracts, Vol. 81, 135512m (abstract of Akhmedov, I. M., etal. (Inst. Georg. Fiz. Khim., Baku, U.S.S.R.) Dokl. Akad. Nauk Az. SSR1974, 30(4), 18-21) discloses the synthesis of the compound having thestructure: ##STR26##

None of the chemical Abstract references discloses compounds which havea close structural relationship to the oxyhydrocarbylnorbornanes of theinstant invention. In any event, the organoleptic properties of thecompounds of the Chemical Abstract references are different in kind fromthose of the oxyhydrocarbylnorbornanes of the instant invention.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is the NMR spectrum for the mixture of oxyhydrocarbylnorbornanes,β,3,3-trimethyl-2-norbornyl-α-buten-γ-one andβ,3,3-trimethyl-2-norbornylidenebutan-γ-one having the structuresrespectively: ##STR27## of our invention produced according to ExampleIA.

FIG. 2 is the Infrared spectrum for the mixture ofoxyhydrocarbylnorbornanes, β,3,3-trimethyl-2-norbornyl-α-buten-γ-one andβ,3,3-trimethyl-2-norbornylidenebutan-γ-one having the structuresrespectively: ##STR28## of our invention produced according to ExampleIA.

FIG. 3 is the NMR spectrum for the oxyhydrocarbylnorbornane,4-(3,3-dimethyl-2-norbornyl)-3-methyl-2-butanone having the structure:##STR29## of our invention produced according to Example IB.

FIG. 4 is the Infrared spectrum for the oxyhydrocarbylnorbornane,4-(3,3-dimethyl-2-norbornyl)-3-methyl-2-butanone having the structure:##STR30## of our invention produced according to Example IB.

FIG. 5 is the NMR spectrum for the oxyhydrocarbylnorbornane,α,β,3,3-tetramethyl-bicyclo[2.2.1]heptane-2-propanol having thestructure: ##STR31## of our invention produced according to Example IC.

FIG. 6 is the Infrared spectrum for the oxyhydrocarbylnorbornane,α,β,3,3-tetramethyl-bicyclo[2.2.1]heptane-2-propanol having thestructure: ##STR32## of our invention produced according to Example IC.

THE INVENTION

It has now been discovered that novel perfume compositions, colognes andperfumed articles including soaps, detergents, cosmetics and powdershaving natural, sweet pine, incense, camphene-like, sweet, green,floral, fruity, dried fruity, ionone-like, orris-like and nasturtiumaromas with dried, woody, piney, sweaty and geranic acid-like nuancesmay be provided by the utilization of one or more of theoxyhydrocarbylnorbornane derivatives having the generic structure:##STR33## wherein at least one of the dashed lines is a carbon-carbonsingle bond and the other of the dashed lines is either a carbon-carbonsingle bond or a carbon-carbon double bond and X is carbonyl or carbinylhaving the structures, respectively: ##STR34## as the "endo" form or the"exo" form or a mixture of "endo" and "exo" forms.

The oxyhydrocarbylnorbornane derivatives of our invention may beproduced according to the following reaction sequence: ##STR35##

Camphene aldehyde is first reacted with methyl ethyl ketone in thepresence of hydrogen chloride. Hydrogen chloride (anhydrous) gas is usedto saturate the mixture of methyl ethyl ketone and camphene aldehyde,thereby causing the production of a mixture of compounds,(β,3,3-trimethyl-2-norbornyl-α-buten-γ-one andβ,3,3-trimethyl-2-norbornylidenebutan-γ-one) having the structures,respectively: ##STR36## The resulting mixture may, if desired, be usedas is for its ability to impart, augment or enhance the aroma of perfumecompositions, colognes or perfumed articles, or it may be used as anintermediate in the preparation of other oxyhydrocarbylnorbornanederivatives of our invention. On the other hand, the resulting mixturemay be separated using, for example, preparative GLC techniques, therebyproducing individually the compound having the structure: ##STR37## andthe compound having the structure: ##STR38##

The reaction of the methyl ethyl ketone with the camphene aldehydepreferably takes place at room temperature and atmospheric pressure, butthe reaction may also be carried out at higher temperatures andpressures, that is, at pressures up to 5 atmospheres and temperatures upto 50° C.

The resulting mixture may thus be hydrogenated in the presence of apalladium-on-carbon catalyst, preferably at room temperature using apressure of between 40 and 80 psig. Higher temperatures and pressuresmay be used if desired but the yield of the reaction product having thestructure: ##STR39## is not affected.

The resulting compound having the structure: ##STR40## may be used forits properties in augmenting or enhancing the aroma of perfumecompositions, perfumed articles and colognes, or it may be used as anintermediate in order to produce the compound having the structure:##STR41## Thus, the compound having the structure: ##STR42## may, ifdesired, be reduced using a lithium aluminum hydride reducing agent inthe presence of an inert solvent, such as anhydrous diethyl ether. Thereduction reaction preferably takes place at reflux which is between 35°and 40° C. at atmospheric pressure. The reaction may also take place athigher temperatures and pressures if desired, e.g. 50° C. and 3atmospheres pressure, but, most conveniently, atmospheric pressure and35°-40° C. suffices for commercial purposes.

Examples of the oxyhydrocarbylnorbornane derivatives of our inventionand their organoleptic properties useful in perfumery are as follows:

    __________________________________________________________________________    Name of Composition                                                                       Structure       Organoleptic Properties                           __________________________________________________________________________    Mixture of β,3,3- trimethyl-2-norbornyl- α-buten-γ-one       and β,3,3- trimethyl-2-norbornyl- idenebutan-γ-one                              ##STR43##      A sweet, floral, dried fruity, ionone-like                                    aroma with a dry, woody, piney nuance.            4-(3,3-dimethyl-2- norbornyl)-3-methyl- 2-butanone                                         ##STR44##      In 10% food grade ethyl alcohol, a natural,                                   sweet pine, incense- like, camphene-like                                      aroma with a sweaty, geranic acid-like note                                   which remains on dry out.                         α,β,3,3-tetra- methyl-bicyclo [2.2.1]heptane- 2-propanol                        ##STR45##      A green floral, sweet ionone-like, orris-                                     like, nasturtium-like aroma.                      __________________________________________________________________________

One or more oxyhydrocarbylnorbornane derivatives of our invention andone or more auxiliary perfume ingredients, including for example, otheralcohols, aldehydes, nitriles, esters, other ketones, cyclic esters andnatural essential oils may be admixed so that the combined odors of theindividual components produce a pleasant and desired fragranceparticularly and preferably in woody and/or floral and/or pineyfragrances. Such perfume compositions usually contain (a) the main noteor the "bouquet" or foundation stone of the composition; (b) modifierswhich round off and accompany the main note; (c) fixatives which includeodorous substances which lend a particular note to the perfumethroughout all stages of evaporation and substances which retardevaporation; and (d) topnotes which are usually low boiling freshsmelling materials.

In perfume compositions, it is the individual components whichcontribute to their particular olfactory characteristics. However, theover-all sensory effect of the perfume composition will be at least thesum total of the effects of each of the ingredients. Thus, one or moreof the oxyhydrocarbylnorbornane derivatives of our invention can be usedto alter, modify or enhance the aroma characteristics of a perfumecomposition, for example, by utilizing or moderating the olfactoryreaction contributed by another ingredient in the composition.

The amount of oxyhydrocarbylnorbornane derivatives of our inventionwhich will be effective in perfume compositions as well as in perfumedarticles and colognes depends on many factors, including the otheringredients, their amounts and the effects which are desired. It hasbeen found that perfume compositions containing as little as 0.01% ofoxyhydrocarbylnorbornane derivatives or even less (e.g., 0.005%) can beused to impart a natural, sweet pine, incense-like, camphene-like,sweet, green, floral, fruity, dried fruity, ionone-like, orris-like andnasturtium-like aroma with dried, woody, piney, sweaty and geranicacid-like nuances to soaps, cosmetics or other products. The amountemployed can range up to 70% of the fragrance components and will dependon considerations of cost, nature of the end product, the effect desiredon the finished product and the particular fragrance sought.

One or more of the oxyhydrocarbylnorbornane derivatives of our inventionare useful [taken alone or together with other ingredients in perfumecompositions] as (an) olfactory component(s) in detergents and soaps,space odorants and deodorants, perfumes, colognes, toilet water, bathpreparations, such as lacquers, brilliantines, pomades and shampoos;cosmetic preparations, such as creams, deodorants, hand lotions and sunscreens; powders, such as talcs, dusting powders, face powders and thelike. When used as (an) olfactory component(s) as little as 1% of theoxyhydrocarbylnorbornane derivatives of our invention will suffice toimpart a natural, sweet pine, incense-like, camphene-like, sweet, green,floral, fruity, dried fruity, ionone-like, orris-like andnasturtium-like aroma with dried, woody, piney, sweaty and geranicacid-like nuances to woody and/or floral and/or piney formulations.Generally, no more than 3% of the oxyhydrocarbylnorbornane derivativesof our invention, based on the ultimate end product, is required in theperfume composition.

In addition, the perfume composition or fragrance composition of ourinvention can contain a vehicle, or carrier for theoxyhydrocarbylnorbornane derivatives. The vehicle can be a liquid suchas a non-toxic alcohol, a non-toxic glycol, or the like. The carrier canalso be an absorbent solid, such as a gum (e.g., gum arabic) orcomponents for encapsulating the composition (such as gelatin).

It will thus be apparent that the oxyhydrocarbylnorbornane derivativesof our invention can be utilized to alter, modify or enhance sensoryproperties, particularly organoleptic properties, such as flavor(s)and/or fragrance(s) of a wide variety of consumable materials.

The following Examples serve to illustrate our invention and thisinvention is to be considered restricted thereto only as indicated inthe appended claims.

All parts and percentages given herein are by weight unless otherwisespecified.

EXAMPLE IA PREPARATION OF MIXTURE OFβ,3,3-TRIMETHYL-2-NORBORNYL-α-BUTEN-γ-ONE ANDβ,3,3-TRIMETHYL-2-NORBORNYLIDENEBUTAN-γ-ONE ##STR46##

Into a 500 ml reaction flask fitted with a reflux condenser, gas exitscrubber, thermometer, gas tube, gas trap and Primol bubbler are charged152 grams (1 mole) of camphene aldehyde and 72 grams (1 mole) of methylethyl ketone. With stirring, the mixture is saturated with anhydroushydrogen chloride gas. Hydrogen chloride gas is continued to be bubbledinto the reaction mass while maintaining the temperature at 23°-29° C.by means of cooling with an isopropanol dry ice bath. The hydrogenchloride bubbling continues over a period of 4 hours. The reaction massis continued to be stirred for a period of 4 hours.

The reaction mass is then poured into 200 ml water yielding two phases:an organic phase and an aqueous phase. The aqueous phase is washed withtwo 200 ml volumes of diethyl ether, and the ether washings are combinedwith the organic phase. The resulting organic phase is then washed withsodium bicarbonate and water to a pH of 6. The reaction mass is thendried over anhydrous magnesium sulfate; and the diethyl ether, which isin excess, is stripped off. The material is then vacuum distilled(boiling point 90°-100° C.) at 0.6 mm Hg yielding 141 grams of oil. Theresulting material is then distilled on a micro Vigreux column afteradding thereto 17 grams of Primol®, yielding the following fractions:

    ______________________________________                                        Frac- Vapor                     Weight % Product                              tion  Temp-   Liquid Temp-                                                                             Vacuum of     Contained                              No.   erature erature    nm Hg  Fraction                                                                             in Fraction                            ______________________________________                                        1     53-70   105-106    5.4    10.1   --                                     2      70     122        2.5    2      --                                     3     103     124        2.6    8      50                                     4     107     124        2.6    11.5   67                                     5     100     123        2.6    8.6    76                                     6     102     132        2.3    11.1   --                                     7     101     137        2.3    9      87                                     8      74     171        2.3    6.3    91                                     9     100     173        2.3    3      41                                     ______________________________________                                    

NMR and IR analysis yield the information that the resulting mixturecontains two compounds having the structures: ##STR47##

The NMR spectrum is set forth in FIG. 1 for this mixture. The Infraredspectrum is set forth in FIG. 2.

The Mass Spectrum is as follows:

    ______________________________________                                        m/e            Relative Intensity                                             ______________________________________                                        39             54                                                             41             80                                                             43             100                                                            53             22                                                             55             27                                                             67             28                                                             79             23                                                             107            29                                                             108            22                                                             109            37                                                             M206           17                                                             ______________________________________                                    

EXAMPLE IB PREPARATION OF4-(3,3-DIMETHYL-2-NORBORNYL)-3-METHYL-2-BUTANONE ##STR48##

Nine grams of the product produced in Example IA, fraction 9, is admixedwith 50 cc of anhydrous isopropyl alcohol and 0.5 grams of a 10%palladium-on-carbon catalyst and the mixture is placed into anautoclave. While maintaining a hydrogen pressure with continuoushydrogen feed at 48-52 psig, the autoclave is shaken for a period of twohours. The autoclave is then opened and the reaction mass is filtered.The resulting reaction mass is dried and solvent stripped to give 8grams of crude product. The resulting material is micro-distilled,yielding 4 fractions and 0.5 grams of residue. GLC (10% SE-30 column,programmed at 80°-220° C. at 8° C. per minute), NMR and IR analysesyield the information that the resulting product has the structure:##STR49##

The NMR spectrum is set forth in FIG. 3. The Infrared spectrum is setforth in FIG. 4.

The Mass Spectral analysis is as follows:

    ______________________________________                                        m/e            Relative Intensity                                             ______________________________________                                        39             31                                                             41             54                                                             43             100                                                            55             20                                                             67             22                                                             69             21                                                             72             23                                                             81             18                                                             93             19                                                             137            17                                                             M208           11                                                             ______________________________________                                    

EXAMPLE IC PREPARATION OFα,β,3,3-TETRAMETHYL-BICYCLO[2.2.1]HEPTANE-2-PROPANOL ##STR50##

Fraction 2 of the reaction product produced according to Example IB (3grams) is admixed wit 0.5 grams of lithium aluminum hydride and 25 cc ofanhydrous diethyl ether in a 50 ml micro-reactor. The reaction mass isrefluxed for a period of 1 hour. When the reaction mass no longerexotherms (at the end of the one hour time period) enough water is addedto dissolve the salts. The reflux temperature is 37° C.

Water is then added to the reaction mass followed by 2 cc concentratedhydrochloric acid to dissolve the salts. The reaction mass now exists intwo phases; an organic phase and an aqueous phase. The aqueous phase iswashed with two volumes of diethyl ether, and the ether extract andorganic phases are combined and dried. A major peak is trapped using GLC(10% Carbowax, programmed at 80°-220° C. at 8° C. per minute). NMR, IRand Mass Spectral analysis yield the information that the resultingproduct has the structure: ##STR51##

The NMR spectrum is set forth in FIG. 5. The Infrared spectrum is setforth in FIG. 6.

The Mass Spectral analysis is as follows:

    ______________________________________                                        m/e            Relative Intensity                                             ______________________________________                                        39             50                                                             41             100                                                            43             60                                                             45             85                                                             55             55                                                             67             58                                                             69             65                                                             81             38                                                             99             70                                                             109            51                                                             M210           21                                                             ______________________________________                                    

EXAMPLE II PINE NEEDLE FORMULATION

The following formulation is prepared:

    ______________________________________                                        Ingredients          Parts by Weight                                          ______________________________________                                        Turpentine gum oil   100                                                      Limonene             70                                                       Gum camphor          10                                                       Isobornyl acetate    50                                                       Borneol              30                                                       Mixture of β,3,3-trimethyl-                                              2-norbornyl-α-buten-γ-                                            one and β,3,3-trimethyl-                                                 2-norbornylidenebutan-                                                        γ-one produced according                                                to Example IA        40                                                       4-(3,3-dimethyl-2-norbornyl)-3-                                               methyl-2-butanone produced                                                    according to Example IB                                                                            100                                                      α,β,3,3-tetramethyl-bicyclo                                        [2.2.1]heptane-2-propanol                                                     produced according to Example IC                                                                   70                                                       ______________________________________                                    

The mixture of β,3,3-trimethyl-2-norbornyl-α-buten-γ-one andβ,3,3-trimethyl-2-norbornylidenebutan-γ-one produced according toExample IA imparts a sweet, floral, dried fruity, ionone-like aroma witha dry, woody, piney nuance to this pine needle oil formulation.

The 4-(3,3-dimethyl-2-norbornyl)-3-methyl-2-butanone produced accordingto Example IB imparts a natural, sweet pine, incense-like andcamphene-like aroma with a sweaty, geranic acid nuance to this pineneedle oil formulation.

The α,β,3,3-tetramethyl-bicyclo[2.2.1]heptane-2-propanol producedaccording to Example IC imparts a green floral, sweet ionone, orris-likeand nasturtium aroma to this pine needle oil formulation.

EXAMPLE III PREPARATION OF A SOAP COMPOSITION

100 Grams of soap chips are mixed with 1 gram of the perfume compositionof Example II until a substantially homogeneous composition is obtained.The perfumed soap composition manifests an excellent pine needlefragrance with green, floral, sweet ionone, orris-like, nasturtium-like,sweet pine, incense and camphene-like notes and sweaty, geranic acidnuances which remain on dry out.

EXAMPLE IV PREPARATION OF A COSMETIC POWDER COMPOSITION

A cosmetic power is prepared by mixing in a ball mill, 100 g of talcumpowder with 0.25 g of the composition prepared according to Example II.It has an excellent pine needle aroma with green floral, sweet ionone,orris-like, nasturtium-like, sweet pine, incense and camphene-like notesand sweaty, geranic acid nuances which remain on dry out.

EXAMPLE V PERFUMED LIQUID DETERGENT

Concentrated liquid detergents (lysine salt of n-dodecyl benzenesulfonic acid as more specifically described in U.S. Pat. No. 3,948,818,issued on Apr. 6, 1976) with intense pine needle aromas are preparedcontaining 0.10%, 0.15% and 0.20% of the perfume composition producedaccording to Example II. The detergents are prepared by adding andhomogeneously mixing the appropriate quantity of perfume oil compositionof Example II. The detergents all possess intense pine needle aromas,with green floral, sweet ionone, orris-like, nasturtium-like, sweetpine, incense and camphene-like notes, with the intensity increasingwith greater concentrations of the formulation of Example II.

EXAMPLE VI PREPARATION OF A COLOGNE AND HANDKERCHIEF PERFUME

The composition produced according to Example II is incorporated into acologne at a concentration of 2.5% in 85% aqueous ethanol. A distinctand definite pine needle fragrance with green floral, sweet ionone,orris-like, nasturtium-like, sweet pine, incense and camphene-like notesis imparted to the cologne. The composition of Example II is also addedto a handkerchief perfume at a concentration of 20% (in 95% aqueousethanol) and a distinct and definite pine needle fragrance with greenfloral, sweet ionone, orris-like, nasturtium-like, sweet pine, incenseand camphene-like notes is imparted to the handkerchief perfume.

EXAMPLE VII PREPARATION OF A SOAP COMPOSITION

100 Grams of soap chips are mixed with 1 gram of the perfume compositionof 4-(3,3-dimethyl-2-norbornyl)-3-methyl-2-butanone prepared accordingto Example IB until a substantially homogeneous composition is obtained.The perfumed soap composition manifests an excellent natural sweet pinearoma with incense and camphene-like notes and sweaty, geranic acidnuances.

EXAMPLE VIII PREPARATION OF A SOAP COMPOSITION

100 Grams of soap chips are mixed with 1 gram ofα,β,3,3-tetramethyl-bicyclo[2.2.1]heptane-2-propanol prepared accordingto Example IC. The perfumed soap composition manifests an excellentgreen floral, sweet ionone, orris-like and nasturtium characteristic.

EXAMPLE IX

A perfume composition is prepared by admixing the following ingredientsin the indicated proportions:

    ______________________________________                                        Ingredient       Amount (Grams)                                               ______________________________________                                        n-Decyl Aldehyde 1                                                            n-Dodecyl Aldehyde                                                                             2                                                            Methyl Nonyl Acetaldehyde                                                                      0.5                                                          Linalool         50                                                           Linalyl Acetate  70                                                           Phenyl Ethyl Alcohol                                                                           100                                                          Petigrain SA     20                                                           Bergamot Oil     30                                                           Alpha Methyl Ionone                                                                            25                                                           4-(3,3-dimethyl-2-norbornyl)-                                                 3-methyl-2-butanone produced                                                  according to Example IB                                                                        10                                                           Cyclized Bicyclo C-12 material                                                produced according to the                                                     process of Example IV of                                                      Canadian Patent 854,225,                                                      issued on October 20, 1970                                                                     5                                                            Isobornyl cyclohexyl alcohol                                                                   10                                                           Benzyl Acetate   25                                                           2-n-Heptyl cyclopentanone                                                                      5                                                                             353.3         (TOTAL)                                        ______________________________________                                    

The foregoing blend is evaluated and found to have a high degree ofrichness and persistence in its novel natural, sweet piney, incense-likeand camphene-like character. This base composition can be admixed withaqueous ethanol, chilled and filtered to produce a finished cologne. Thecologne so prepared has a natural, sweet pine, incense and camphene-likearoma with a sweaty, geranic acid note which remains on dry out. Thisnote is quite desirable and valuable. The base composition can also beused to scent soap or other toilet goods such as lotions, aerosols,sprays and the like.

EXAMPLE X

A perfume composition is prepared by admixing the following ingredientsin the indicated proportions:

    ______________________________________                                        Ingredient       Amount (Grams)                                               ______________________________________                                        n-Decyl Aldehyde 1                                                            n-Dodecyl Aldehyde                                                                             2                                                            Methyl Nonyl Acetaldehyde                                                                      0.5                                                          Linalool         50                                                           Linalyl Acetate  70                                                           Phenyl Ethyl Alcohol                                                                           100                                                          Petigrain SA     20                                                           Bergamot Oil     30                                                           Alpha Methyl Ionone                                                                            25                                                           α,β,3,3-tetramethyl-                                               bicyclo[2.2.1]heptane-                                                        2-propanol produced                                                           according to Example IC                                                                        10                                                           Cyclized Bicyclo C-12 material                                                produced according to the                                                     process of Example IV of                                                      Canadian Patent 854,225,                                                      issued on October 20, 1970                                                                     5                                                            Isobornyl cyclohexyl alcohol                                                                   10                                                           Benzyl Acetate   25                                                           2-n-heptyl cyclopentanone                                                                      5                                                                             353.3         (TOTAL)                                        ______________________________________                                    

The foregoing blend is evaluated and found to have a high degree ofrichness and persistence in its novel green floral, sweet ionone-like,orris-like and nasturtium-like quality. This base composition can beadmixed with aqueous ethanol, chilled and filtered to produce a finishedcologne. The cologne so prepared has a green floral, sweet ionone-like,orris-like and nasturtium-like aroma. The base composition can also beused to scent soap or other toilet goods such as lotions, aerosols,sprays and the like.

EXAMPLE XI PREPARATION OF A COSMETIC POWDER COMPOSITION

A cosmetic powder is prepared by mixing in a ball mill 100 g of talcumpowder with 0.25 g ofα,β,3,3-tetramethyl-bicyclo[2.2.1]heptane-2-propanol prepared accordingto Example IC. It has an excellent green floral, sweet ionone-like,orris-like and nasturtium-like aroma.

What is claimed is:
 1. A process for preparing a mixture of compoundshaving the structures: ##STR52## comprising the steps of reacting methylethyl ketone with camphene aldehyde in the presence of anhydroushydrogen chloride whereby the anhydrous hydrogen chloride iscontinuously and intimately admixed with a mixture of methyl ethylketone and camphene aldehyde, said reaction being carried out at from 1up to 5 atmospheres pressure and from ambient temperature up to 50° C.2. The process of claim 1 comprising the additional step of reacting themixture of compounds having the structures: ##STR53## with hydrogen inthe presence of a palladium-on-carbon catalyst thereby producing acompound having the structure: ##STR54## wherein each of the wavy linesrepresents C-H and C-C single bonds in a "cis" or "trans" configurationwith respect to the norbornyl moiety, the reaction taking place at apressure of between 40 and 80 psig at ambient temperature.
 3. Theprocess of claim 2 comprising the additional step of reacting thecompound having the structure: ##STR55## with lithium aluminum hydridethereby producing a compound having the structure: ##STR56## whereineach of the wavy lines represents C-H and C-C single bonds in a "cis" or"trans" configuration with respect to the norbornyl moiety, the reactiontaking place in the presence of an inert solvent at atmospheric pressureup to three atmospheres pressure and from 35° up to 50° C.